JP2011256372A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition in which the roughness on the surface of an insulating layer is small in a wet roughening process and on which a plating conductor layer having sufficient peel strength can be formed.SOLUTION: The resin composition includes (A) a siloxane imide resin having a functional group, and (B) a biphenyl type epoxy resin.

Description

  The present invention relates to a resin composition containing a specific siloxane imide resin and an epoxy resin.

  Polyimide resins having excellent heat resistance are widely used in the electronics field, aerospace field, and the like. For example, a material having both heat resistance and low elasticity has been developed by introducing a siloxane structure into the polyimide resin (Patent Document 1). However, the description about the specific application was limited.

Japanese Patent Laid-Open No. 2002-12666

  The problem to be solved by the present invention is to provide a resin composition that can form a plated conductor layer having a small roughness on the surface of the insulating layer and sufficient peel strength on the wet roughening step. is there.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention in a resin composition containing a specific siloxane imide resin and an epoxy resin.

（式中、Ｒ１は４価の有機基を示し、Ｒ２はヘキサフルオロイソプロパノール基を有する２価のジアミン残基、Ｒ３は２価のシロキサンジアミン残基を示す。式（１）で表される繰り返し単位の一分子中の繰り返し数Ｍは１以上１００以下（１≦Ｍ≦１００）の整数であり、式（２）で表される繰り返し単位の一分子中の繰り返し数Ｎは１以上１００以下（１≦Ｎ≦１００）の整数である。）
で表される繰り返し単位を有することを特徴とする上記［１］又は［２］に記載の樹脂組成物。
［４］樹脂組成物中の不揮発成分を１００質量％とした場合、（Ａ）官能基を有するシロキサンイミド樹脂の含有量が、１０〜８０質量％であることを特徴とする上記［１］〜［３］のいずれかに記載の樹脂組成物。
［５］樹脂組成物中の不揮発成分を１００質量％とした場合、（Ｂ）ビフェニル型エポキシ樹脂の含有量が、３〜５０質量％であることを特徴とする上記［１］〜［４］のいずれかに記載の樹脂組成物。
［６］更に、（Ｃ）硬化剤を含有することを特徴とする上記［１］〜［５］のいずれかに記載の樹脂組成物。
［７］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有する接着フィルム。
［８］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有するプリプレグ。
［９］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有する多層プリント配線板。
［１０］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有する半導体装置。
［１１］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有するウェハレベルパッケージ。
［１２］上記［１］〜［６］のいずれかに記載の樹脂組成物を含有するＬＥＤ搭載回路基板。 That is, the present invention includes the following contents.
[1] A resin composition comprising (A) a siloxane imide resin having a functional group and (B) a biphenyl type epoxy resin.
[2] (A) The siloxane imide resin having a functional group is one or more selected from a hexafluoroisopropanol group-containing siloxane imide resin, a phenol group-containing siloxane imide resin, and a vinyl group-containing siloxane imide resin. The resin composition as described in [1] above, wherein
[3] (A) A siloxane imide resin having a functional group is represented by the following formulas (1) and (2):

(Wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent siloxane diamine residue. Repeat represented by Formula (1)) The repeating number M in one molecule of the unit is an integer of 1 to 100 (1 ≦ M ≦ 100), and the repeating number N in one molecule of the repeating unit represented by the formula (2) is 1 to 100 ( 1 ≦ N ≦ 100).)
The resin composition as described in [1] or [2] above, having a repeating unit represented by
[4] The above-mentioned [1], wherein the content of the siloxane imide resin having a functional group (A) is 10 to 80% by mass when the nonvolatile component in the resin composition is 100% by mass. [3] The resin composition according to any one of [3].
[5] The above [1] to [4], wherein the content of the (B) biphenyl type epoxy resin is 3 to 50% by mass when the nonvolatile component in the resin composition is 100% by mass. The resin composition in any one of.
[6] The resin composition according to any one of [1] to [5], further comprising (C) a curing agent.
[7] An adhesive film containing the resin composition according to any one of [1] to [6].
[8] A prepreg containing the resin composition according to any one of [1] to [6].
[9] A multilayer printed wiring board containing the resin composition according to any one of [1] to [6].
[10] A semiconductor device containing the resin composition according to any one of [1] to [6].
[11] A wafer level package containing the resin composition according to any one of [1] to [6].
[12] An LED-mounted circuit board containing the resin composition according to any one of [1] to [6].

  Resin composition containing a specific siloxane imide resin and an epoxy resin, and capable of forming a plated conductor layer having sufficient peel strength on the surface of the insulating layer having a low roughness in the wet roughening step. I can now offer things.

  The present invention is a resin composition comprising (A) a siloxane imide resin having a functional group and (B) a biphenyl type epoxy resin.

[(A) Siloxane-imide resin having a functional group]
The (A) functional group-containing siloxane imide resin used in the present invention is not particularly limited, and includes hexafluoroisopropanol group (hereinafter referred to as HFA group) -containing siloxane imide resin, phenol group-containing siloxane imide resin, Examples include vinyl group-containing siloxane imide resins. Among these, from the viewpoints of compatibility and heat resistance, HFA group-containing siloxane imide resins and phenol group-containing siloxane imide resins are preferable, and HFA group-containing siloxane imide resins are more preferable. Moreover, what has a repeating unit represented by the following Formula (1) and (2) is still more preferable. A functional group here means what can react with an epoxy resin or a peroxide and can form a crosslinked structure.

In the formula, R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having an HFA group, and R3 represents a divalent siloxane diamine residue. The number M of repeating units in one molecule of the repeating unit represented by the formula (1) is preferably an integer of 1 to 100 (1 ≦ M ≦ 100). Moreover, it is preferable that the repeating number N in 1 molecule of the repeating unit represented by Formula (2) is an integer of 1 or more and 100 or less (1 ≦ N ≦ 100).

Examples of the tetravalent organic group represented by R1 include those having the following structures.

In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , or C (CCl ₃ ) ₂ . To express.
In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

  Examples of the divalent diamine residue having an HFA group represented by R2 include those having the following structures.

In the formula, A has the same meaning as described above. J shows the integer of 1-4. K represents an integer of 1 to 6. P and Q each independently represent an integer of 0 to 2, and 1 ≦ (P + Q) ≦ 4.
In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

  Examples of the divalent siloxane diamine residue represented by R3 include those having the following structures.

(Wherein R4 and R5 each independently represents an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having a number of 1 to 5 or a phenoxy group, a, b and c each independently represent 0 or an integer of 1 or more, and b + c ≧ 0 and a + b + c ≧ 60. The hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.)

  The siloxane imide resin in this invention can be manufactured by making the tetrabasic dianhydride represented by Formula (3) react with the diamine compound represented by Formula (4) and (5).

(Wherein R1, R2 and R3 have the same meanings as described above.)

  The tetravalent organic group represented by R1 of the tetrabasic acid dianhydride represented by the formula (3) is as described above. Specific examples of the tetravalent organic group represented by R1 include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid. Dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) -bis- (phthalic dianhydride), 4 , 4′-oxydiphthalic dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) -bis- (phthalic dianhydride), 1,3-dihydro-1,3-dioxo-5 -Isobenzofurancarboxylic acid (1-methylethylidene) -di-4,1-phenylene ester, ethylene glycol bisanhydro trimellitate, 3,4,9,10-perylenetetracarboxylic dianhydride, 9,9-bis (3,4) -Dicarboxyphenyl) fluorene dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Xene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan -1,3-dione and the like. These tetrabasic dianhydrides can be used in combination of two or more.

Examples of the diamine compound having an HFA group represented by the formula (4) include those represented by the following formula.

In the formula, A has the same meaning as described above. J shows the integer of 1-4. K represents an integer of 1 to 6. P and Q each independently represent an integer of 0 to 2, and 1 ≦ (P + Q) ≦ 4.
In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
In formula (4-b), the amino groups on the naphthalene ring may be bonded to the same benzene ring or may be bonded to different benzene rings. Similarly, when there are a plurality of HFA groups, each may be bonded to the same benzene ring, or may be bonded to different benzene rings.
The diamine compound represented by the formula (4-a) can be produced according to a known method described in International Publication No. 2006/043501. The diamine compound represented by the formula (4-c) can be produced according to a known method described in International Publication No. 2006/041115. The diamine compound represented by the formula (4-b) is prepared by reacting a corresponding naphthalenediamine compound with a hexagonal compound according to a known method described in International Publication No. 2006/043501 and International Publication No. 2006/041115. It can be produced by reacting fluoroacetone or hexafluoroacetone trihydrate and introducing an HFA group onto the naphthalene ring. These diamine compounds having an HFA group can be used in combination of two or more.

  Examples of the diaminosiloxane represented by the formula (5) include those represented by the following formula.

  In the formula, R4 and R5 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number. An alkoxy group of 1 to 5 or a phenoxy group; a, b and c each independently represent 0 or an integer of 1 or more, and b + c ≧ 0 and a + b + c ≧ 60. In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

  The siloxane structure in the present invention is preferably a structure represented by the following formula (5b).

  In the formula, Re and Rf each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, or a phenoxy group, m is an integer of 60 or more, and a repeating unit For each, Re or Rf may be different.

  Examples of the diaminosiloxane represented by the formula (5a) include 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis (3-aminobutyl). ) -1,1,2,2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,1,3,3-tetra Methyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetra Phenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetra Methyl-1,3- (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3- Bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,3,3,5,5-hexamethyl- 1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5 , 5-Tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5 -Aminopentyl) trisiloxane, , 1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5 -Bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3 5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like. These diaminosiloxanes may be used alone or in combination of two or more.

  You may use together diamine compounds other than the diamine compound represented by Formula (4) and (5), combining 1 type (s) or 2 or more types. The diamine compound can be represented by the following formula (6).

(In the formula, R11 represents a divalent organic group other than a divalent diamine residue having a HFA group and a divalent siloxane diamine residue.)
The diamine compound is not particularly limited. For example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diamino-2,5- Diamine compounds containing one benzene ring such as dimethylbenzene and 1,4-diamino-2,5-dihalogenobenzene, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3, , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-aminodiphenylmethane 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 2,2-bis (4-aminophenyl) propane, 2, 2-bis (3-aminophenyl) propane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis ( 3-amino-4-methylphenyl) hexafluoropropane, 1,1′-bis (4-aminophenyl) cyclohexane, o-dianisidine, o-tolidine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 3,3 ′, 5 5′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetramethyl-4, 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobiphenyl, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ' , 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-methylene-bis (2-ethyl-6-methylaniline) ), 3,3′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3 '-Diethyl-4 , 4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diamino Diamine compounds containing two benzene rings such as diphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene, 1,4-bis (4-amino Phenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,4-bis (3-aminophenyl) benzene, α, α'-bis (4-aminophenyl) -1,4- Diamine compounds containing three benzene rings such as isopropylbenzene and α, α'-bis (4-aminophenyl) -1,3-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′- (4-aminophenoxy) biphenyl, 4,4 ′-(3-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, , 9-bis (3-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, 5,10- Diamine compounds containing four or more benzene rings such as bis (4-aminophenyl) anthracene, 1,3-diaminopyrene, 1,6-diaminopyrene, 4,4′-methylenebis (cyclohexylamine), 4,4′- Diamine compounds having an alicyclic structure such as methylenebis (2-methylcyclohexylamine), 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-dia Diamine compounds having a linear hydrocarbon structure such as nododecane, diamine compounds having a dimer amine structure such as trade name Versamine 551 (manufactured by Cognis Japan Co., Ltd.), trade names Jeffamine D-230, D-400, D-2000 Polyoxyalkylenediamine structures such as D-4000, XTJ-500, XTJ-501, XTJ-502, HK-511, XTJ-504, XTJ-542, XTJ-533, and XTJ-536 (manufactured by Huntsman Corporation). Examples thereof include diamine compounds.

The diaminosiloxane represented by the formula (5) preferably has an NH ₂ equivalent in the range of 400 to 6000 g / mol, more preferably in the range of 400 to 2500 g / mol, and more preferably in the range of 400 to 1000 g / mol. A range is more preferable. When the NH ₂ equivalent is larger than this range, the hydrophobicity of the resin becomes too strong due to the large molecular weight of the siloxane structure and the compatibility with the thermosetting resin deteriorates. The difference in polarity of the siloxane part becomes too large, making it difficult to stably synthesize the resin. On the other hand, when the NH ₂ equivalent is smaller than this range, the molecular weight of the siloxane structure is small, and it is difficult to obtain sufficient flexibility. Moreover, the thing containing a phenyl group is preferable at the point with good miscibility with a thermosetting resin.

When the tetrabasic acid dianhydride represented by the formula (3) and the diamine compound represented by the formulas (4) and (5) are used together (the diamine compound represented by the formula (6) is used in combination, the formula (4) To the total of the diamine compounds represented by formula (6) is not particularly limited, and either one may be excessive, but preferably the molecular weight of the resulting resin is increased. From the viewpoint of improving mechanical properties, it is preferable that the total number of functional group equivalents of all diamine compounds used in the reaction is substantially equal to the number of functional group equivalents of tetrabasic acid dianhydride. Specifically, when the number of functional group equivalents of the acid anhydride group of the tetrabasic acid dianhydride used is X, and the number of functional group equivalents of the amino group of all amine compounds used is Y, 0 ≦ | (XY) The reaction is preferably performed under the condition of | /X≦0.3, and more preferably the reaction is performed under the condition of 0 ≦ | (XY) | /X≦0.1.
The number of functional group equivalents X (mol) of the acid anhydride group is expressed by the formula X = B1 / A1, where A1 (g / mol) is the functional group equivalent of the acid anhydride group and B1 (g) is charged. Can be obtained. That is, the functional group equivalent represents the molecular weight of the compound per functional group, and the functional group equivalent number represents the number of functional groups per compound mass (preparation amount).

  Similarly, the functional group equivalent A2 (g / mol) of the amino group of the diamine compound containing the HFA group represented by the formula (4), the charge amount is B2 (g), and the diaminosiloxane represented by the formula (5) Functional group equivalent A3 (g / mol) of amino group, charge amount B3, functional group equivalent A4 (g / mol) of amino group of the diamine compound represented by formula (6), charge amount B4 (g) Then, Y = (B2 / A2) + (B3 / A3) + (B4 / A4) can be obtained. The diamine compound represented by the formula (6) is an optional component, and when it is not contained, (B4 / A4) = 0 in the above formula.

  On the other hand, since the charging ratio of the diamine compounds of formulas (4) and (5) is reflected in the content of the siloxane structure and the content of HFA groups in the obtained resin, these two values are arbitrarily set. By setting, the range of the charging ratio of the diamine compounds of formulas (4) and (5) is inevitably determined. First, about the quantity of the siloxane structure contained in resin obtained, it is preferable that a mass ratio will be 40-90 mass%, and it is more preferable that it will be 50-80 mass%. When the proportion of the siloxane structure is larger than 90% by mass, the resulting resin has high adhesiveness and is difficult to handle, and conversely when it is smaller than 40% by mass, the flexibility of the resin becomes poor.

  The content Z (mass%) of the siloxane structure can be obtained by the following formula: Z (mass%) = {B3 / (B1 + B2 + B3 + B4-B5)} × 100 where B5 is the mass of water desorbed by imidization. . Here, B5 can be obtained by the equation B5 = 18 × W, where W is the smaller of the above X or Y values. Moreover, the diamine compound represented by Formula (6) is an arbitrary component, and when it is not contained, B4 = 0 in the above formula.

  The upper limit of the content of the siloxane structure is preferably 80% by mass, more preferably 75% by mass, still more preferably 70% by mass, and particularly preferably 65% by mass from the viewpoint of maintaining heat resistance at high temperatures. On the other hand, the lower limit of the content of the siloxane structure is preferably 50% by mass, more preferably 54% by mass, and still more preferably 58% by mass from the viewpoint of expressing flexibility.

  In addition, the upper limit of the functional group equivalent of the HFA group (hereinafter referred to as HFA group equivalent) of the resulting siloxane imide resin is too small to cure the resin composition using this resin. From the viewpoint of preventing insufficient curing when it is applied, it is preferably 10,000 g / mol, more preferably 8500 g / mol, still more preferably 6000 g / mol, still more preferably 5000 g / mol, and even more preferably 4000 g / mol. preferable. On the other hand, the lower limit value of the HFA group equivalent of the resulting polyimide resin is that the content of the siloxane structure is inevitably reduced due to the high crosslinking density when the resin composition is cured due to the inclusion of many HFA groups. In view of this, 1000 g / mol is preferable, 1500 g / mol is more preferable, 2000 g / mol is further preferable, and 2500 g / mol is still more preferable from the viewpoint of preventing the flexibility of the cured product from being lowered. The HFA group equivalent V (g / mol) of the polyimide resin is determined by the formula V (g / mol) = (B1 + B2 + B3 + B4-B5) ÷ (B2 / H) where HFA group equivalent of the HFA group-containing diamine compound is H. be able to. The diamine compound represented by the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

  The terminal of the siloxane imide resin varies depending on the reaction ratio of the tetrabasic acid dianhydride and the diamine compound, but is considered to be a dicarboxyl group in which an amino group, an acid anhydride group, or an acid anhydride group is opened.

  Although reaction operation is not specifically limited, For example, performing heat | fever dehydration imidation in a polymerization solution is more preferable from the simplicity of work. Specifically, first, in an inert gas atmosphere, a solvent azeotropic with water, such as toluene and xylene, is added to a solvent in which a diamine compound having an HFA group and siloxane diamine are dissolved. Next, tetrabasic acid dianhydride is added and reacted at 80 ° C. or lower, preferably 0 to 50 ° C. for 1 to 24 hours to obtain a polyamic acid solution. The obtained polyamic acid solution is heated at 100 to 200 ° C., preferably 150 to 200 ° C., and the polyimide solution can be obtained by ring-closing while removing water azeotropically with toluene. At this time, the reaction was completed when it was confirmed that almost the theoretical amount of water was distilled off and that no outflow of water was observed. On the other hand, apart from this method, the polyamic acid dehydration ring closure reaction can also be carried out at a low temperature using an acetic anhydride / pyridine mixed solution.

  The reaction solvent used in the reaction is not particularly limited as long as it does not react with the raw material and the obtained resin. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, α-methyl- γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, ethylene carbonate, propylene carbonate, ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl isobutyl ketone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and the like can be mentioned, preferably cyclohexanone, γ-butyrolac Tons. These solvents may be used alone or in combination of two or more. In particular, it is more preferable to use an aromatic hydrocarbon solvent such as petroleum naphtha in combination with a solvent such as cyclohexanone or γ-butyrolactone.

  Further, the obtained siloxane imide resin solution can be put into a poor solvent such as water or methanol to precipitate a polymer, and further dried, and then re-dissolved in a solvent according to the use.

  The upper limit of the number average molecular weight (Mn) of the siloxane imide resin in the present invention is preferably 50000, more preferably 40000, and more preferably 30000 from the viewpoint of preventing the viscosity of the resin composition from increasing and handling properties from decreasing. Is more preferable, 25000 is still more preferable, and 20000 is particularly preferable. On the other hand, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10,000, and even more preferably 15,000, from the viewpoint of expressing the flexibility of the resin composition. The upper limit of the weight average molecular weight (Mw) of the polyimide resin in the present invention is preferably 50000, more preferably 40000, and more preferably 30000 from the viewpoint of preventing the viscosity of the resin composition from increasing and handling properties from decreasing. Further preferred. On the other hand, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10,000, further preferably 15000, and particularly preferably 20000, from the viewpoint of expressing the flexibility of the resin composition. The number average molecular weight and the mass average molecular weight are values measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight and mass average molecular weight determined by the GPC method are LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K manufactured by Showa Denko KK as a column. -804L / K-804L was measured at a column temperature of 40 ° C using a solution of 0.4% by mass of lithium bromide dissolved in N-methylpyrrolidone as a mobile phase, and calculated using a standard polystyrene calibration curve. can do.

From the viewpoint of improving the curability of the resin composition, the upper limit of the content of the siloxane imide resin is preferably 80% by mass and more preferably 75% by mass when the nonvolatile component in the resin composition is 100% by mass. Preferably, 70 mass% is further more preferable, and 65 mass% is still more preferable. On the other hand, the lower limit of the content of the siloxane imide resin is preferably 10% by mass, preferably 25% by mass, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of ensuring the flexibility of the resin composition. Is more preferred, 30% by weight is still more preferred, 35% by weight is even more preferred, 40% by weight is particularly preferred, 45% by weight is particularly preferred, and 50% by weight is particularly preferred.

[(B) Biphenyl type epoxy resin]
The (B) biphenyl type epoxy resin used in the present invention is not particularly limited, but a tetramethyl biphenyl type epoxy resin and a biphenyl dimethylene type epoxy resin are preferable, and among them, the biphenyl represented by the following formula (7) A dimethylene type epoxy resin is more preferable. These may be used alone or in combination of two or more.

（式中ｎは１〜１０の整数を示す。）

(In the formula, n represents an integer of 1 to 10.)

Examples of commercially available biphenyl type epoxy resins include “NC3100”, “NC3000”, “NC3000L”, “NC3000H”, “NC3000FH” manufactured by Nippon Kayaku Co., Ltd., “YX4000H” manufactured by Japan Epoxy Resin Co., Ltd. “YL6121” and the like.

From the viewpoint of preventing the cured product from becoming brittle, the upper limit of the content of the biphenyl type epoxy resin is preferably 50% by mass and 35% by mass when the nonvolatile component in the resin composition is 100% by mass. More preferably, 20% by mass is further preferable, 15% by mass is even more preferable, 13% by mass is even more preferable, and 12% by mass is particularly preferable. On the other hand, the lower limit of the content of the biphenyl type epoxy resin is preferably 3% by mass and more preferably 5% by mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of improving plating adhesion. Preferably 7 mass% is still more preferable.

  The peel strength of the cured product of the resin composition of the present invention can be grasped by the measurement method described in <Measurement of peel strength (peel strength) of plated conductor layer> described later. The upper limit of the peel strength of the cured product of the resin composition of the present invention is preferably 1.0 kgf / cm, more preferably 2.0 kgf / cm, further preferably 5.0 kgf / cm, and further 10.0 kgf / cm. Even more preferred. On the other hand, the lower limit of the peel strength of the cured product of the resin composition of the present invention is preferably 0.2 kgf / cm, more preferably 0.3 kgf / cm, and still more preferably 0.4 kgf / cm.

  The surface roughness of the cured product of the resin composition of the present invention can be grasped by a measuring method described in <Measurement of surface roughness (Ra value) after roughening> described later. The upper limit of the surface roughness of the cured product of the resin composition of the present invention is preferably 700 nm, more preferably 600 nm, and even more preferably 500 nm. On the other hand, the lower limit of the surface roughness of the cured product of the resin composition of the present invention is preferably 100 nm, more preferably 70 nm, and even more preferably 50 nm.

[(C) Curing agent]
The resin composition of the present invention can improve the curability and water resistance of the resin composition by further containing (C) a curing agent. The curing agent is not particularly limited as long as it cures an epoxy resin. For example, a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, a benzoxazine compound, an amine imide compound, a cyanate. Examples include ester compounds. Of these curing agents, phenolic compounds are particularly preferable.

As a phenol type compound, what has a 2 or more phenol group is preferable. For example, bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolac resin, cresol novolac resin, paraxylylene modified phenol resin, metaxylylene / paraxylylene modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin And polycyclic aromatic ring-modified phenol resins, naphthalene ring-containing phenol resins, biphenyl type phenol resins, triazine structure-containing phenol novolac resins, and the like. These may be used alone or in combination of two or more. Among these, a biphenyl type phenol resin is preferable.

As the carboxylic acid compound, those having two or more carboxyl groups are preferred. Examples include organic acids such as terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methyl nadic acid, dodecyl succinic acid, chlorendic acid, maleic acid, and adipic acid. It can be used alone or in combination of two or more.

  As the acid anhydride compound, those having one or more acid anhydride groups are preferable. Examples include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, maleic anhydride, etc. These can be used alone or in admixture of two or more.

  The amine compound is used as a curing agent for causing an addition reaction with the epoxy resin or anionic polymerization of the epoxy resin itself. For example, tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2 -IM- which is an imidazole silane compound having both imidazole and silanol moieties, and imidazoles such as undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, etc. 1000 (Nikko Metal Co., Ltd.) and IS-1000 (Nikko Metal Co., Ltd.), or 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4 ′ -Diaminodiphenyl ether, 4,4'-diaminobenzophenone, , 3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, Aromatic amine compounds such as 3,3′-aminodiphenylmethane and 3,4′-diaminodiphenylmethane; aliphatic amine compounds such as m-xylylenediamine, diethylenetriamine and tetraethylenepentamine; and melamine resins, 2 -Triazine compounds such as vinyl-4,6-diamino-s-triazine, dicyandiamide and the like.

  As the benzoxazine-based compound, those having two or more benzoxazine moieties are preferable, and examples thereof include Ba type benzoxazine and Bb type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.).

  The amine imide compound is obtained by reacting a maleimide compound and an amine compound, and in particular, one having two or more secondary amino groups is preferable. For example, Techmite E2020 (manufactured by Printec Co., Ltd.), etc. Is mentioned.

  As the cyanate ester-based compound, those having two or more cyanate groups are preferable, and examples thereof include Primaset BADCY, Primaset BA230S, and Primaset LECY manufactured by Lonza Japan Co., Ltd.

The content when the curing agent is blended is preferably 1 to 15% by mass, more preferably 2 to 13% by mass, and more preferably 3 to 11% by mass when the nonvolatile component in the resin composition is 100% by mass. % Is more preferable. If the content of the curing agent is too small, curing tends to be insufficient and chemical resistance, heat resistance and the like tend to be inferior, and if too large, flexibility tends to be insufficient.

[(D) Inorganic filler]
The resin composition of the present invention can further reduce the thermal expansion coefficient of the insulating layer by further containing (D) an inorganic filler. The inorganic filler is not particularly limited, for example, silica, alumina, barium sulfate, talc, mica, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, Examples thereof include aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. In addition, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, and hollow silica is preferable, and fused silica is more preferable. Further, the silica is preferably spherical. You may use these 1 type or in combination of 2 or more types.

  The average particle diameter of the inorganic filler is not particularly limited, but the upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 1 μm or less from the viewpoint of improving the insulation reliability. 0.7 μm or less is more preferable. On the other hand, the lower limit value of the average particle size of the inorganic filler is 0.05 μm from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing when the resin composition is a resin composition varnish. The above is preferable.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  The inorganic filler in the present invention is preferably one that has been surface treated with a surface treatment agent such as an epoxy silane coupling agent, an aminosilane coupling agent, or a titanate coupling agent to improve its moisture resistance. You may use these 1 type or in combination of 2 or more types. As the surface treatment agent, aminosilane-based cups such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyl trimethoxysilane, etc. Epoxy silanes such as ring agents, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents, mercaptosilane coupling agents such as mercatopropyltrimethoxysilane, mercatopropyltriethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane Silane coupling agents such as lan, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3,3 , 5,5-hexametacyclotrisilazane and other organosilazane compounds, butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (Dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, Tra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) Bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri Dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) Titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate coupling agents such as titanates.

  When the inorganic filler is blended, the content varies depending on the properties required of the resin composition when the nonvolatile component in the resin composition is 100 mass%, but is preferably 5 to 60 mass%. 10-50 mass% is more preferable, and 15-40 mass% is still more preferable. If the content of the inorganic filler is too small, the coefficient of thermal expansion of the cured product tends to increase, and if the content is too large, the cured product tends to become brittle and the peel strength tends to decrease.

[(E) Curing accelerator]
The resin composition of this invention can harden an epoxy resin etc. efficiently by containing (E) hardening accelerator further. Examples of the (E) curing accelerator used in the present invention include an imidazole curing accelerator, an amine curing accelerator, and a phosphonium curing accelerator. You may use these 1 type or in combination of 2 or more types.

The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2 -Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyano Ethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2, 4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl- Examples thereof include imidazole compounds such as 2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. You may use these 1 type or in combination of 2 or more types.

The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1 , 8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), amine compounds such as dicyandiamide, and the like. You may use these 1 type or in combination of 2 or more types.

The phosphonium curing accelerator is not particularly limited, and examples thereof include triphenylphosphine, triphenylphosphonium triphenylborate, and tetraphenylphosphonium tetraphenylborate. You may use these 1 type or in combination of 2 or more types.

Although there is no restriction | limiting in particular in content of a hardening accelerator, The range of 0.005-1 mass% is preferable with respect to 100 mass% of non-volatile components in a resin composition, The range of 0.01-0.5 mass% Is more preferable. If it is less than 0.005% by mass, curing tends to be slow and a long thermosetting time is required, and if it exceeds 1% by mass, the storage stability of the resin composition tends to decrease and the coefficient of thermal expansion tends to increase. Become.

[(F) Epoxy resin (excluding biphenyl type epoxy resin)]
The resin composition of this invention can improve sclerosis | hardenability and water resistance by containing (F) epoxy resin (except biphenyl type epoxy resin) further. (F) Epoxy resin (excluding biphenyl type epoxy resin) is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy Resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin , Trimethylol type epoxy resin, halogenated epoxy resin and the like. You may use these 1 type or in combination of 2 or more types.

Examples of commercially available epoxy resins include “jER828EL” and “YL980” (bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., “jER806H” and “YL983U” (bisphenol F manufactured by Japan Epoxy Resin Co., Ltd.). Type epoxy resin), Japan Epoxy Resin Co., Ltd. “RXE21” (hydrogenated bisphenol A type epoxy resin), Japan Epoxy Resin Co., Ltd. “871”, “191P” (glycidyl ester type epoxy resin), Japan Epoxy Resin “604”, “630LSD” (glycidylamine type epoxy resin) manufactured by KK, “HP4032”, “HP4032D” (naphthalene type bifunctional epoxy resin) manufactured by DIC, “PB-” manufactured by Daicel Chemical Industries, Ltd. 3600 "(with butadiene structure Epoxy resin), DIC Corporation "HP7200H", Daicel Chemical Industries, Ltd. Celoxide "2021P", "2081", "3000" (alicyclic epoxy resin), Toto Kasei Co., Ltd. "ZX-" 1658 "(cyclohexanedimethanol type epoxy resin), Japan Epoxy Resin Co., Ltd." 157S70 "(special novolac type epoxy resin), Japan Epoxy Resin Co., Ltd." YX8800 "(anthracene skeleton-containing epoxy resin), Japan Epoxy Resin Co., Ltd. “YL7410”, DIC Co., Ltd. “EXA-4816”, Toto Kasei Co., Ltd. “YDC-1312”, “YSLV-80XY”, “YSLV-120TE”, “ZX-1598A”, "ESN-475V" etc. are mentioned.

  In the resin composition of the present invention, when the nonvolatile component in the resin composition is 100% by mass, the total amount of (B) biphenyl type epoxy resin and (F) epoxy resin (excluding biphenyl type epoxy resin) is 3 to 3. It is preferably 50% by mass, more preferably 5 to 35% by mass, and even more preferably 7 to 20% by mass. When the total amount of (B) biphenyl type epoxy resin and (F) epoxy resin (excluding biphenyl type epoxy resin) is out of this range, the curability of the resin composition tends to decrease.

[(G) Rubber particles]
The resin composition of the present invention can further improve the roughening property and improve the plating peel strength of the cured product by further containing (G) rubber particles. The rubber particles used in the present invention are, for example, those that do not dissolve in an organic solvent used when preparing the varnish of the resin composition and are incompatible with an epoxy resin that is an essential component. Accordingly, the rubber particles exist in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Preferable examples of rubber particles that can be used in the present invention include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade name, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.

  1-10 mass% is preferable with respect to 100 mass% of non volatile components in a resin composition, and, as for content of a rubber particle, 2-5 mass% is more preferable.

[(H) Flame retardant]
The resin composition of the present invention can impart flame retardancy by further containing (H) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organic phosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Co., Inc. Reefos 30, 50, 65, 90, 110, Fine Techno Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ, Clariant (made by Hokuko Chemical Co., Ltd.) Phosphoric acid ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., FX289 compounds manufactured by Tohto Kasei Co., Ltd., phosphorus-containing epoxy resins such as FX305, phosphorus such as ERF001 manufactured by Tohto Kasei Co., Ltd. And a phosphorus-containing epoxy resin such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.

[Other ingredients]
In the resin composition of the present invention, other components can be blended within the range where the effects of the present invention are exhibited. Examples of other components include thickeners such as Orben (manufactured by Shiraishi Kogyo Co., Ltd.) and Benton (manufactured by Leox), silicone-based, fluorine-based or acrylic antifoaming agents, leveling agents, imidazole-based, thiazole. -Based, triazole-based adhesion promoters, silane coupling agents and other surface treatment agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus-containing compounds, bromine-containing compounds, hydroxylation Examples thereof include flame retardants such as aluminum and magnesium hydroxide, antioxidants such as phosphorus antioxidants and phenolic antioxidants, and peroxides such as hexamethylene triperoxide diamine and metachloroperbenzoic acid.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.

  The use of the resin composition of the present invention is not particularly limited, but includes an insulating resin sheet such as an adhesive film and a prepreg, a multilayer printed wiring board, an adhesive release film, a solder resist, an underfill material, a coverlay, a die bonding material, and a semiconductor. It can be used in a wide range of applications where a resin composition is required, such as a sealing material, hole-filling resin, and component-filling resin. Especially, it can use suitably in order to form an insulating layer in manufacture of a multilayer printed wiring board and a semiconductor package. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

[Adhesive film]
The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent combining 1 type (s) or 2 or more types.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for 3 to 10 minutes. It is preferable.

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. After laminating the protective film, it can also be stored in a roll.

[Multilayer printed wiring board using adhesive film]
Next, an example of a method for producing a multilayer printed wiring board using the adhesive film produced as described above will be described.

  First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107). 9.9 × 10 ⁴ N / m ² ), and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

Moreover, the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.

The pressing condition is that the degree of vacuum is usually 1 × 10 −2 MPa or less, preferably 1 × 10 −3 MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2, and the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Roughening treatment is performed with an oxidizing agent such as sulfuric acid or nitric acid to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

[Prepreg]
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material made of fibers by a hot melt method or a solvent method, and heating and semi-curing. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As the sheet-like reinforcing substrate made of fibers, for example, those made of fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

  In the hot melt method, the resin is not coated in an organic solvent, but once coated on a coated paper with good releasability from the resin and laminated to a sheet-like reinforcing substrate, or the resin is dissolved in an organic solvent. In this method, the prepreg is produced by directly coating the sheet-like reinforcing substrate with a die coater. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.

[Multilayer printed wiring board using prepreg]
Next, an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described. One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and vacuum press laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the adhesive film, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

[Adhesive release film]
The pressure-sensitive adhesive release film of the present invention is a method known to those skilled in the art, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by heating or blowing hot air to dry the organic solvent and cure the resin composition itself. At this time, the adhesive force and peeling force of the resin composition layer can be controlled by adjusting the heating conditions.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent combining 1 type (s) or 2 or more types.

  The drying and curing conditions are not particularly limited, but at least the content of the organic solvent in the resin composition layer after drying and curing is 5% by mass or less, and lightly rubbed with a waste impregnated with an organic solvent such as acetone. It is preferable to dry and cure to such an extent that the resin does not dissolve. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, a resin composition layer is formed by heating a varnish containing 30 to 60% by mass of an organic solvent at 50 to 200 ° C. for 3 to 90 minutes. Can do.

  Although the thickness of the resin composition layer formed in an adhesive peeling film is not specifically limited, It is preferable to have a thickness of 1-100 micrometers.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. The support may be subjected to a surface treatment such as a mud treatment or a corona treatment.

  Although the thickness of a support body is not specifically limited, 5-150 micrometers is preferable and 10-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The pressure-sensitive adhesive release film can be stored in a roll shape after laminating the protective film.

This adhesive release film is manufactured by selecting a heat-resistant film such as a polyimide film as a support, thereby protecting the circuit surface of the semiconductor chip in the resin molding process of semiconductor package manufacture and the glass substrate in the transistor formation of flexible display manufacture. It can be used for fixing to a material.

[Method of manufacturing semiconductor package using adhesive release film]
Next, an example of a method for manufacturing a semiconductor package using the adhesive release film manufactured as described above will be described. First, an adhesive release film is manufactured in advance using a heat-resistant polyimide film as a support. Subsequently, the semiconductor chip is adhered on the resin composition layer of the adhesive release film so that the circuit surface is in contact with the resin composition layer. Subsequently, the resin is molded from above the semiconductor chip and cured. The mold conditions can be arbitrarily applied according to the work of the mold resin, and can be carried out, for example, in a general range of 150 to 220 ° C. Finally, by peeling the adhesive release film, a semiconductor package can be manufactured without soiling the circuit surface with the mold resin.

[Semiconductor device]
A semiconductor device can be manufactured by using the resin composition of the present invention. The semiconductor device of the present invention is manufactured by bonding a semiconductor element to a connecting electrode portion on a multilayer printed wiring board and sealing with resin. However, the multilayer printed wiring board of the present invention can be used, and the present invention The resin composition can be used for resin sealing. The mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like. Examples of the resin sealing method include a transfer molding method using a solid resin composition, a dispensing method and a printing method using a resin varnish, and a method of laminating and sealing a thick adhesive film on a semiconductor. It is done.

[Wafer level package]
By using the resin composition of the present invention, a wafer level package with excellent low warpage can be produced, and a wafer level package with a single area layer can also be produced. Various structures have been devised for the wafer level package, and can be roughly divided into a fan-in structure and a fan-out structure.

An example of a method for manufacturing a fan-in structure wafer level package includes a method including the following steps.
(1) A step of forming circuits and electrode pads on a silicon wafer.
(2) A step of laminating the adhesive film of the present invention on a silicon wafer.
(3) A step of curing the adhesive film, drilling, performing desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.
(4) A step of repeating (2) and (3) from above the rewiring layer as necessary.
(5) A step of forming solder balls on the rewiring layer.
(6) A step of performing dicing.

As an example of the manufacturing method of the wafer level package of another fan-in structure, the method described in the patent 3618330 is mentioned, for example, The method including the following processes is mentioned.
(1) A step of creating a silicon wafer on which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A step of forming a columnar electrode on the upper surface of the electrode pad portion on the silicon wafer.
(3) A step of bonding and curing the adhesive film of the present invention from the columnar electrode surface side to form an insulating layer.
(4) A step of appropriately polishing and removing the upper surfaces of the insulating layer and the columnar electrode to expose the upper surface of the columnar electrode.
(5) A step of forming a solder ball on the upper surface of the exposed columnar electrode.
(6) A step of performing dicing.

An example of a method for manufacturing a fan-out structure wafer level package includes a method including the following steps.
(1) A step of dicing a silicon wafer to create chip pieces.
(2) A step of fixing the chip pieces on the support via an adhesive film.
(3) A step of laminating the adhesive film of the present invention from the chip piece side.
(4) A step of curing the adhesive film, drilling, performing desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.
(5) A step of further laminating an adhesive film as necessary.
(6) A step of forming solder balls on the rewiring layer.

As an example of the manufacturing method of the wafer level package of another fanout structure, the method described in Unexamined-Japanese-Patent No. 2005-167191 is mentioned, for example, The method including the following processes is mentioned.
(1) A step of creating a silicon wafer on which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A step of creating semiconductor chip pieces through dicing.
(3) The semiconductor chips are widely arranged and fixed via the adhesive film on the support in such a positional relationship that the distance between the semiconductor chips has a sufficient space for forming a fan-out ball array in a later step. Process.
(4) A step of laminating the adhesive film of the present invention so as to fill the space between the semiconductor chips from the surface side on which the semiconductor chips are fixed.
(5) A step of curing the adhesive film, etching the insulating layer on the pad of the semiconductor chip, forming an opening, and forming a conductive layer in the opening.
(6) A step of forming a fan-out pattern and an electrode on the insulating layer using a photoresist and forming a solder ball on the electrode pad.

[LED circuit board]
By using the resin composition of this invention, the LED mounting circuit board excellent in high adhesiveness and withstand voltage property can be produced. Various structures have been devised for the LED-mounted circuit board. For example, the following steps can be included.
(1) Create a flexible circuit board patterned on one side. Examples of the base material of the flexible circuit board include a whitened polyimide film having a function as a light reflecting material, an LCP film, or a blackened polyimide film having an effect of conspicuously emitting an LED light emitting portion.
(2) An insulating protective film is formed on the flexible circuit board. As the insulating protective film, a whitened insulating film having a high light reflection function or a blackened insulating film having an effect of conspicuous LED light emitting portion is used. This insulating film is formed by 1) forming an ink obtained by adding a white pigment or a black pigment to the resin composition, screen-printing on the circuit surface and curing it, and 2) forming a white pigment or black on the resin composition. An adhesive film is prepared by applying a pigment added to a support, punched into a predetermined pattern, and bonded and cured on a circuit surface. 3) Whitened polyimide film or LCP film or black An adhesive film using the converted polyimide film as a support can be prepared, punched into a predetermined pattern shape, and bonded to a circuit surface and cured to form.
(3) The adhesive film of the present invention is bonded to the back surface of the flexible circuit board to form a laminate.
(4) A through hole for LED mounting is formed in the laminate.
(5) A heat sink is bonded to the adhesive film side of the laminate. The heat sink is exemplified by an aluminum plate or a copper plate.
(6) The adhesive film is cured.
(7) On the heat sink exposed at the bottom of the through hole of the laminate, a high thermal conductive paste is applied to mount the LED.
(8) The high thermal conductive paste is cured, and the wires of the LED and the flexible circuit board are connected by wire bonding.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

<Sample adjustment method and measurement method>
First, the sample adjustment method and measurement method will be described.

<Preparation of sample for measuring peel strength and surface roughness (Ra value)>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 manufactured by MEC Co., Ltd.

(2) Lamination of adhesive film The adhesive film created in Examples and Comparative Examples was laminated on both surfaces of the inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . Lamination was performed for 30 seconds under conditions of a temperature of 120 ° C., a pressure of 7 kgf / cm 2, and an atmospheric pressure of 5 mmHg or less.

(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, and the resin composition was cured under a curing condition of 180 ° C for 30 minutes to form an insulating layer.

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is immersed in a swelling dip seculigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 5 minutes at 60 ° C., and then roughened. As a chemical solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 5 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. Were dipped in 40 g of reduction Shoryushin securigant P for 5 minutes. The circuit board after this roughening treatment was designated as Sample 1.

(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner circuit board is immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution for 30 minutes. A 1.5 μm electroless copper film was formed. This was heated at 150 ° C. for 30 minutes and annealed, then washed with acid, the phosphor-containing copper plate was used as the anode, and electrolytic copper plating was performed at a cathode current density of 2.0 A / dm 2 for 12 minutes. Formed. Thereafter, annealing was further performed at 180 ° C. for 30 minutes. The conductor plating thickness was about 25 μm. This circuit board was designated as sample 2.

<Measurement of surface roughness (Ra value) after roughening>
Using a non-contact type surface roughness tester (WYKO NT3300 manufactured by BEIKO INSTRUMENTS CO., LTD.), The Ra value was obtained from a numerical value obtained by setting the measurement range to 121 μm × 92 μm using a VSI contact mode and a 50 × lens. And it measured by calculating | requiring the average value of the measurement point chosen at random. In Table 1, those that could not be measured were shown as "-", and those that were not measured were shown as "x".

<Measurement of peel strength (peel strength) of plated conductor layer>
Sample 2 was evaluated according to JIS C6481. Make a notch of 10mm width and 100mm length in the conductor layer of the circuit board, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL), The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured. In Table 1, those that could not be measured were indicated as “−”.

[Synthesis Example 1]
In a 500 mL separable flask equipped with a moisture receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA) 20 parts by mass, 70.9 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, 72.9 parts by mass (amine equivalent 665) of diaminosiloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2, Under a nitrogen stream, 2.7 parts by mass of 6-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -1,5-naphthalenediamine (hereinafter referred to as HFA-NAP) was added. The reaction was carried out with stirring at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by mass of a polyimide resin (A1) having an HFA group was produced. In this case, the content of the siloxane structure in the resin is 78.0% by mass, and the HFA equivalent is 8392 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by mass of lithium bromide was dissolved, and the whole was adjusted to 5 g. When the GPC measurement was performed using this adjustment solution, it was Mn = 230668 and Mw = 30512.

[Synthesis Example 2]
In a 500 mL separable flask equipped with a moisture meter connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 20 parts by mass of BTDA, 70.1 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diaminosiloxane 61.5 parts by mass of X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent of 665) and 7.4 parts by mass of HFA-NAP were added and stirred at 45 ° C. for 2 hours under a nitrogen stream. Reaction was performed. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by mass of a polyimide resin (A2) having an HFA group was produced. In this case, the content of the siloxane structure in the resin is 70.6% by mass, and the HFA equivalent is 2881 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by mass of lithium bromide was dissolved, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 13135 and Mw = 35245.

[Synthesis Example 3]
In a 500 mL separable flask equipped with a moisture meter connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 20 parts by mass of BTDA, 74.6 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diaminosiloxane 62.3 parts by mass (amine equivalent 655) of X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 4.1 parts by mass of HFA-NAP were added and stirred at 45 ° C. for 2 hours under a nitrogen stream. Reaction was performed. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by mass of a polyimide resin (A3) having an HFA group was produced. In this case, the content of the siloxane structure in the resin is 70.6% by mass, and the HFA equivalent is 5458 g / mol.

[Synthesis Example 4]
In a 500 mL separable flask equipped with a moisture meter, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 30 parts by mass of BTDA, 75.9 parts by mass of γ-butyrolactone, 10 parts by mass of toluene, diaminosiloxane 49.9 parts by mass (amine equivalent 440) of KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), 10.1 parts by mass of Versamine 551 (amine equivalent 250) and 5.95 parts by mass of HFA-NAP were added to add nitrogen. The reaction was performed by stirring at 45 ° C. for 2 hours under an air stream. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by mass of a polyimide resin (A4) having an HFA group was produced. In this case, the content of the siloxane structure in the resin is 53.8% by mass, and the HFA equivalent is 3817 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by mass of lithium bromide was dissolved, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, it was Mn = 18200 and Mw = 32792.

[Synthesis Example 5]
In a 500 mL separable flask equipped with a moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 23 parts by mass of BTDA, 29.5 parts by mass of γ-butyrolactone, and 29.5 parts by mass of ipsol 150 , 7 parts by mass of toluene, 49.1 parts by mass (amine equivalent 440) of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) were charged, and the reaction was performed by stirring at 45 ° C. for 1 hour under a nitrogen stream. Subsequently, 2.6 parts by mass of 4,4′-diamino-3,3′-dimethyldiphenylmethane (hereinafter referred to as C-100) was added, and the reaction was performed by stirring at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 50% by weight of a polyimide resin (A5) having no functional group was produced. In this case, the content of the siloxane structure in the resin is 68.0% by weight.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. In addition, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. When GPC measurement was performed using this prepared solution, Mn = 38052 and Mw = 110120.

[Examples 1-4, Comparative Examples 1-4]
Epoxy resin, resin synthesized according to the above synthesis examples 1-5, if necessary, curing agent, curing accelerator, inorganic filler are mixed in the blending amounts shown in the table (indicated by mass part of solid content), and centrifugal defoaming mixing A resin composition was obtained by mixing with stirring using a machine (trade name “Nentaro Awatake”, manufactured by Shinky Co., Ltd.). As the epoxy resin, ESN-475V (manufactured by Toto Kasei Co., Ltd.), YL7410 (manufactured by Japan Epoxy Resin Co., Ltd.), NC3000H, NC3000FH (manufactured by Nippon Kayaku Co., Ltd.), EXA4816 (manufactured by DIC Corporation) are used. It was. As a curing agent, biphenyl type phenol novolac resin MEH-7851-4H (manufactured by Meiwa Kasei Co., Ltd.), EXB9500 (manufactured by DIC Corporation), dicyandiamide epicure DICY7 (manufactured by Japan Epoxy Resin Co., Ltd.) was used. As the curing accelerator, imidazole P200H50 (manufactured by Japan Epoxy Resin Co., Ltd.) was used. As the inorganic filler, spherical silica SO-C2 (manufactured by Admatechs) and IXE770D (manufactured by Toagosei Co., Ltd.) were used. In addition, a solvent was mixed and used as necessary. Next, the obtained resin composition was applied on a 38 μm-thick PET film subjected to a release treatment using a die coater so that the thickness after drying was 40 μm. After the application, an adhesive film having a resin composition layer formed thereon was produced by drying at 75 to 120 ° C. for 12 minutes.

Table 1 shows the results.

From the results shown in Table 1, when (A) a siloxane imide resin having a functional group and (B) a biphenyl type epoxy resin were used in combination, the high peel strength and the low surface roughness were compatible. I understand. On the other hand, when the (B) biphenyl type epoxy resin was not blended as in Comparative Examples 1 and 2, the surface roughness became very large and the plating was swollen, so that the peel strength could not be measured. In Comparative Example 3, since the siloxane imide resin having a functional group (A) was not blended, the adhesive film became brittle, and the peel strength and surface roughness could not be evaluated. Since Comparative Example 4 was a siloxane imide resin having no functional group, the plating did not adhere and swollen, and the peel strength could not be measured.

By using a resin composition containing a specific siloxane imide resin and an epoxy resin, forming a plated conductor layer having a small roughness on the surface of the insulating layer and sufficient peel strength on the wet roughening step. Resin compositions, adhesive films, prepregs, and multilayer printed wiring boards can be provided. Furthermore, electric products such as semiconductor devices, computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these devices can be provided.

Claims (12)

A resin composition comprising (A) a siloxane imide resin having a functional group and (B) a biphenyl type epoxy resin. (A) The siloxane imide resin having a functional group is one or more selected from a hexafluoroisopropanol group-containing siloxane imide resin, a phenol group-containing siloxane imide resin, and a vinyl group-containing siloxane imide resin. The resin composition according to claim 1. (A) A siloxane imide resin having a functional group is represented by the following formulas (1) and (2):

(Wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent siloxane diamine residue. Repeat represented by Formula (1)) The repeating number M in one molecule of the unit is an integer of 1 to 100 (1 ≦ M ≦ 100), and the repeating number N in one molecule of the repeating unit represented by the formula (2) is 1 to 100 ( 1 ≦ N ≦ 100).)
The resin composition according to claim 1, wherein the resin composition has a repeating unit represented by: The content of the siloxane imide resin having a functional group (A) is 10 to 80% by mass when the nonvolatile component in the resin composition is 100% by mass. 2. The resin composition according to item 1. The content of (B) biphenyl type epoxy resin is 3 to 50% by mass when the nonvolatile component in the resin composition is 100% by mass, according to any one of claims 1 to 4. The resin composition as described. Furthermore, (C) a hardening | curing agent is contained, The resin composition of any one of Claims 1-5 characterized by the above-mentioned. The adhesive film containing the resin composition of any one of Claims 1-6. The prepreg containing the resin composition of any one of Claims 1-6. The multilayer printed wiring board containing the resin composition of any one of Claims 1-6. The semiconductor device containing the resin composition of any one of Claims 1-6. A wafer level package containing the resin composition according to claim 1. The LED mounting circuit board containing the resin composition of any one of Claims 1-6.